The present invention relates to reactive dye compounds. In particular the present invention relates to reactive dye compounds having improved dye-bath Exhaustion (E) and improved dye-fibre covalent Fixation (F).
Reactive dye compounds are known in the art for dyeing various substrates. Such substrates include for example proteinaceous materials such as keratin, e.g. found in hair, skin and nails and various animal body parts such as horns, hooves and feathers, and other naturally occurring protein containing materials, e.g. silk and saccharide-derived materials such as those derived from cellulose or cellulose derivatives, e.g. natural products such as cotton, and synthetic fibres such as polyamides.
Examples of classes of such reactive dyes which are well known in the art include dyes containing a mono- or dichloro- or fluoro-1,3,5-triazinyl group, mono- or dichloro or fluoro-pyrimidyl group, beta-halogen-propionyl group, beta-halogenoethyl-sulphonyl group, beta-halogenoethylsulphamyl group, chloroacetyl amino, beta-(chloro-methyl)-beta-sulphatoethylsulphamyl group, or a vinyl sulphonyl group.
In the case of the dyes containing a triazinyl group or a pyrimidyl group, in place of the reactive halogen atoms one can use other groups which dissociate in the presence of alkali. Canadian Patent 771632, for example, discloses examples of such other groups including sulphonic acid, thiocyanate, sulphophenoxy, sulphophenyl thio, nitrosulphophenoxy groups, and quaternary ammonium groups.
Dyes and Pigments 14, 1990, pages 239-263, xe2x80x9cSynthesis and Application of Reactive Dyes with Heterocyclic Reactive Systemsxe2x80x9d discloses fibre reactive dyes containing monochloro- or dichloro- pyrimidine heterocycle with quaternary ammonium substituents.
There are many different types of commercially-available reactive dyes for dyeing cellulosic and polyamide-type substrates. However, a critical problem still facing the textile dye industry today is the significant level of dyestuff material which remains in the effluent waste water after the dyeing process is finished. The industry measure for this problem is known as dye-bath Exhaustion (E). A high Exhaustion value for a particular dye compound means that a low level of spent dye remains in the effluent after the dyeing process is complete, while a low Exhaustion value means that a high level of spent dye remains in the effluent. There is clearly a need therefore for new dye compounds which have higher Exhaustion Values compared with commercially available dye compounds, and which provide benefits in terms of reducing levels of spent dyestuff in effluent water.
As well as having a high Exhaustion Value, it is also important for a dye compound to have a high dye-fibre covalent Fixation Value (F). The Fixation Value (F) of a reactive dye compound is a measure of the extent of covalent bonding with the substrate based on the dye originally absorbed during the dyeing process. Thus 100% Fixation means that 100% of the dye covalently bonds to the substrate. Thus, there is clearly a need to provide dye compounds having increased Fixation Values. A high Fixation Value can result in a simplification of the post dyeing xe2x80x9csoaping off processxe2x80x9d traditionally associated with fiber reactive dye compounds. In particular, a high Fixation Value can result in a reduced time spent on the xe2x80x9csoaping off processxe2x80x9d together with a reduced cost.
It has now been surprisingly found that a new class of fibre reactive dye compounds comprising a nitrogen-containing heterocycle substituted with at least one thio-derivative, such as thioglycolate, and at least one quaternized nitrogen derivative, such as nicotinate, exhibit significantly increased values of Exhaustion (E) and Fixation (F). These dyes can be used on a wide variety of substrates. They are particularly useful for cellulosic substrates, such as cotton, and show significant improvements in terms of reducing spent dyestuff in effluent, increasing dye affinity to the substrate, increasing the efficiency of the dye-substrate covalent reaction, and simplifying the post dyeing xe2x80x9csoaping off processxe2x80x9d traditionally associated with reactive dyes. In addition, the compounds of the present invention provide significantly more intense dyeings, and can be used for both high and low temperature dyeing, hence reducing the cost of the dyeing process. Furthermore, the compounds of the present invention can be used together with specific chromophores for cellulose substrate dyeing leading to significantly reduced levels of salt needed for dyeing.
According to the present invention there is provided a reactive dye compound comprising:
(a) at least one chromophore moiety;
(b) at least one nitrogen-containing heterocycle;
(c) a linking group to link each chromophore moiety to each nitrogen-containing heterocycle;
characterised in that the nitrogen-containing heterocycle is substituted with at least one thio-derivative and at least one quatemized nitrogen derivative.
The compounds of the present invention exhibit increased Exhaustion (E) and Fixation (F) values and provide improvements in terms of reducing spent dyestuff in effluent, increasing dye affinity to the substrate, increasing the efficiency of the dye-substrate covalent reaction, ability to carry out the dyeing process at room temperature as well as at elevated temperatures, and simplifying the post dyeing xe2x80x9csoaping off processxe2x80x9d traditionally associated with fiber reactive dyes. In addition, the compounds of the present invention provide significantly more intense dyeings, i.e. greater colour intensity in the dyed substrate.
As used herein the term xe2x80x9creactive dyexe2x80x9d means a dye containing one or more reactive groups, capable of forming covalent bonds with the substrate to be dyed, or a dye which forms such a reactive group in situ.
As used herein the term xe2x80x9cExhaustionxe2x80x9d in relation to reactive dyes means the percentage of dye which is transferred from a solution of the dye to the substrate to be treated at the end of the dyeing process, before rinsing and soaping. Thus 100% Exhaustion means that 100% of the dye is transferred from the dye solution to the substrate.
As used herein the term xe2x80x9cFixationxe2x80x9d in relation to reactive dyes means the percentage of dye which covalently bonds with the substrate, based on the dye originally absorbed during the dyeing process. Thus 100% Fixation means that 100% of the dye absorbed is covalently bonded with the substrate.
The compounds of the present invention comprise a chromopbore moiety and a nitrogen-containing heterocycle linked via a linking group. The nitrogen-containing heterocycle has at least one thio-substituent and at least one quatemized nitrogen derivative.
The reactive dye compounds herein can comprise one or more chromophore moieties. In reactive dye compounds comprising two or more chromophore moieties these can be the same or different. Preferably the reactive dye compounds herein comprise from one to three chromophore moieties.
Any chromophore moieties suitable for use for dyeing substrates can be used in the present invention. The term chromophore as used herein means any photoactive compound and includes any coloured or non-coloured light absorbing species, eg. fluorescent brighteners, UV absorbers, IR absorbing dyes.
Suitable chromophore moieties for use in the dye compounds herein include the radicals of monoazo, disazo or polyazo dyes or of heavy metal complex azo dye derived therefrom or of an anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthene, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide dye.
Suitable chromophore moieties for use in the dye compounds herein include those disclosed in EP-A-0,735,107 (Ciba-Geigy), incorporated herein by reference, including the radicals described therein which contain substituents customary for organic dyes, such as sulphonate substituents which enhance the water-soluble properties of the dye compound.
Most preferred chromophore D groups for use herein are polysulphonated azo chromophores such as those present in Procion (RTM) dyes commercially available from BASF, Drimalan (RTM) dyes commercially available from Clariant, Drimarene (RTM) dyes commercially available from Clariant and Levafix (RTM) commercially available from Dystar.
The reactive dyes of the present invention comprise at least one nitrogen containing heterocyclic moiety. In reactive dye compounds containing two or more nitrogen containing heterocycles these can be the same or different. Preferably the reactive dye compounds herein comprise from one to three nitrogen containing heterocycles. At least one of the nitrogen containing heterocycle moieties herein is substituted with at least one thio-derivative and at least one quaternized nitrogen derivative.
Suitable nitrogen containing heterocycles for use herein include monocyclic, bicyclic or polycyclic, unsaturated heterocycles containing at least one nitrogen heteroatom. When monocyclic rings are used, they are preferably selected from unsaturated rings having from about 3 to about 7 ring atoms, especially 5 or 6 ring atoms, comprising from about 1 to about 3 nitrogen heteroatoms, preferably 2 or 3 nitrogen heteroatoms. When bicyclic heterocycles are used, they preferably comprise an unsaturated nitrogen containing heterocycle having 3 to 7 ring atoms, preferably an unsaturated nitrogen containing heterocycle having 5 or 6 ring atoms comprising 1 or 2 nitrogen atoms, fused to a 5 to 7 membered carbocycle preferably a 6-membered unsaturated carbocycle. When bicyclic heterocycles are used, the thio- and quaternized nitrogen substituents are preferably attached to the nitrogen containing heterocyclic ring.
Preferred for use herein are 5 or 6 membered unsaturated nitrogen containing monocyclic heterocyclic rings comprising 2 or 3 nitrogen heteroatoms or bicyclic rings containing a 5 or 6 membered unsaturated heterocyclic ring containing 2 nitrogen heteroatom fused to a 6 membered unsaturated carbocycle.
Examples of suitable heterocycles for use herein include, but are not necessarily limited to triazine, pyrimidine, quinoxaline, pyrimidinone, phthalazine, pyridazone and pyrazine.
Preferred for use in the compounds herein are triazine, pyrimidine and quinoxaline.
The compounds herein further comprise a linking moiety to link each nitrogen-containing heterocycle to each chromophore moiety. Any linking moieties suitable for use in dyeing substrates can be used in the present invention. Preferably the linking moiety is selected from NR, NRCxe2x95x90O, C(O)NR, NRSO2 and xe2x80x94SO2NR wherein R is H or C1-C4 alkyl which can be substituted by halogen, preferably fluorine or chlorine, hydroxyl, cyano, C1-C4 alkoxy, C2-C5 alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato. When the heterocycle is a triazine or pyrimidine a preferred linking moiety is NR, preferably where R is H or C1-C4 alkyl, more preferably where R is H or CH3, especially H. When the heterocycle is quinoxaline or phthalazine, a preferred linking moiety is NRCxe2x95x90O, where R is H or C1-C4 alkyl, more preferably where R is H or CH3, especially H.
Suitable thio-derivatives for use herein include, but are not necessarily limited to groups having the formula SRxe2x80x2 wherein Rxe2x80x2 is selected from H or alkyl or preferably short chain alkyl (preferably less than about 6 carbon atoms), alkanol, alkyl carboxylate, alkylamide, alkylsulphonate, alkyl phosphonate, alkyl thiosulphonate, alkylamine, alkyl thiosulphate, aryl sulphonate, aryl carboxylate, aryl phosphate, aryl amine, cyanates, sulphonates, branched alkyl thio carboxylates, branched alkanol thiols, guanides, alkyl-(xcex1-amino-xcex1-carboxylate, (di) thio alkyl esters of glycerol, alkyl thiol alkyl esters of glycerol, alkyl esters, mono thio diesters, thiol alkyl esters of ethylene glycol, alkyl thiol alkyl ester of ethylene glycol and alkyl thiolipoates. Preferably R is selected from alkyl carboxylates and alkanols.
Examples of suitable thio-derivatives include SRxe2x80x2 groups where Rxe2x80x2 is selected from C1-C4 alkyl, (CH2)nCOOH, (CH2)nCONH2, (CH2)nSO3H, (CH2)nCOOM, (CH2)nPO3H, (CH2)nOH, (CH2)nSSO3xe2x88x92, (CH2)nNRxe2x80x32, (CH2)nN+Rxe2x80x33, PhSSO3xe2x88x92, PhSO3H, PhPO3H, PhNRxe2x80x32, PhN+Rxe2x80x33, xe2x80x94CN, SO3xe2x88x92, (CH2)2CH(SH)Rxe2x80x3(CH2)3COOH, xe2x80x94CH2CHOHCH2SH, and 
xe2x80x94CH2CH2NH2.
n is an integer in the range of 1 to 4 wherein within the same molecule n is not necessarily the same integer; and M is a cation of alkaline earth metal, alkali metal, NH4+ or NRxe2x80x33+ and wherein Rxe2x80x3 is C1-C4 alkyl.
Preferred thio-derivatives for use herein have the formula SRxe2x80x2 wherein Rxe2x80x2 is (CH2)nCOOH, (CH2)nOH, and (COOH)CH2CH2(COOH), wherein n is an integer from 1 to 4.
Especially preferred for use herein are thioglycolate (Rxe2x80x2=CH2COOH) thioethanol (Rxe2x80x2=(CH2)2OH) and succinate (Rxe2x80x2=(COOH)CH2CH2(COOH)), especially thioglycolate.
Suitable quatemized nitrogen derivatives for use herein can be represented by Q+ wherein Q is selected from amines, saturated or unsaturated, substituted or unsubstituted nitrogen containing heterocycles having from about 3 to about 8 ring members and comprising at least one nitrogen heteroatom. Preferred substituents are carboxylates, amides, C1-C4 alkyl and alkyl carboxylates.
Particularly preferred for use herein are Q groups selected from:
NRxe2x80x33, 
(CH3)2Nxe2x80x94NH2;
N(CH3)2CH2COOH (dimethylaminobetaine);
N(CH3)2(CH2)nNH2;
N(CH3)2(CH2)nN+Rxe2x80x33;
N(CH3)2CH2CONH2;
wherein Rxe2x80x3 is C1-C4 alkyl and n is an integer of from 1 to 4.
Particularly preferred quatemized nitrogen derivatives for use herein are nicotinate, diazabicyclooctane (DABCO), dimethylaminobetaine and isonicotinate, especially nicotinate.
The quaternized nitrogen derivative is attached to the nitrogen-containing heterocycle via its tertiary nitrogen atom.
Preferred reactive dye compounds of the present invention may be represented by the following formula (I): 
wherein: D is a chromophore group as described hereinabove;
L is a linking moiety as defined herein, preferably selected from NR, NRCxe2x95x90O, NRSO2, wherein R is as defined hereinabove;
Z is a nitrogen containing heterocycle as defined hereinabove;
SRxe2x80x2 is a thio-derivative as described hereinabove,
Q+ is a quatemized nitrogen derivative as described hereinabove,
A is halogen, preferably chlorine or fluorine;
and salts and esters thereof.
Other preferred reactive dye compounds of the present invention can be represented by the formula (II): 
wherein: B is a chromophore D as defined above, bifunctional chromophore, or other organic radical suitable for use in place of a chromophore such as those taught in the art (see for example EP-A-0,735,107), provided that the reactive dye compound contains at least one chromophore group. Suitable B groups included xcex2-sulphatoethylsulphonyl benzene, vinyl sulphonyl benzene, chloroethylsulphonyl benzene, xcex2-s-thiosulphatoethyl sulphonyl benzene, di(ethylsulphonyl) chiomophore
L, Z, Q, A are as defined hereinabove;
J is selected from S, O, NH
K is selected from Q30 , halogen
Lxe2x80x2 is a linking group which can be any suitable biradical linking group suitable for use in dye compounds and is preferably selected from B wherein B is as defined above, C1-C4 alkyl, esters having the formula (Al), diesters having the formula (Al), amides having the formula (Al), diamides having the formula (Al) wherein A is (CH2)0-2xe2x80x94(C(O)xe2x80x94J)0-1xe2x80x94(CH2)1-4xe2x80x94(Jxe2x80x94C(O))0,1xe2x80x94(CH2)0-2xe2x80x94(Jxe2x80x94C(O))xe2x80x94(C1-C4)xe2x80x94(C(O)xe2x80x94J)xe2x80x94 where J is O, NH or S;
C1-C4 dialkyl sulphides, C1-C4 dialkylsulphoxides, C1-C4 dialkyl sulphones, C1-C4 dialkyl carboxylates, or groups having the formula: 
Suitable examples of Lxe2x80x2 include succinate, diethyl sulphide, xcex2-sulphatoethylsulphonyl benzene, vinyl sulphonyl benzene, chloroethylsulphonyl benzene, xcex2-s-thiosulphatoethyl sulphonyl benzene, di(ethylsulphonyl) chromophore, ethyl, diethylsulphone, isopropanol.
Another preferred reactive dye according to the present invention can be represented by compounds of the formula (III): 
wherein: B, L, Z, Q, J, K and A are as defined above and Lxe2x80x3 is a linking group which can be any suitable triradical linking group suitable for use in dye compounds and is preferably selected from glycerol, diethylenetriarnine and N,Nxe2x80x2,Nxe2x80x3 tripropanoylaminohexahydrotriazine provided that the reactive dye compound comprises at least one chromophore group.
Another preferred reactive dye compound according to the present invention can be represented by compounds of the formula (IV): 
wherein: each of D, L, Z, Rxe2x80x2, Q are as defined above;
V and W are independently selected from NR, or SRxe2x80x2 wherein R and Rxe2x80x2
are as defined hereinabove, Q+, halogen.
Another preferred reactive dye compound according to the present invention can be represented by compounds of the formula (V): 
wherein: each of B, Z, Q, A, Rxe2x80x2, L, V and W are as defined above, provided that the reactive dye compound contains at least one chromophore group.
In the above formulations it is to be noted that within each compound each of the defined groups may be the same or different. For example in formula IV one of the Z groups may be pyrimidine and the other Z group may be triazine.
The present invention furthermore relates to processes for the preparation of dyes herein. In general, dyes having the formula (I) can be prepared by reacting suitable precursors of the dye of formula (I) with one another, at least one of which contains a group D-L-Z, wherein D, L and Z are as defined above, at least one of which contains an Rxe2x80x2 group (wherein Rxe2x80x2 is as defined above) and at least one of which contains a Q group (wherein Q is as defined above).
For example, dye compounds of the invention having a formula (I) wherein Z is a triazine heterocycle can be prepared by reacting one mole of dichlorotriazine dye, such as those commercially available from BASF under the tradename Procion (RTM), with a one mole of a suitable reactant containing an SRxe2x80x2 group and then reacting the intermediate dye compounds obtained with one mole of a suitable reactant containing a Q group.
Dye compounds of the invention having a formula (I) wherein Z is a pyrimidine heterocycle can be prepared by reacting a difluoromonochloro pyrimidine dye such as those commercially available from Clariant under the tradenames Drimalan F (RTM) and Drimarene R or K (RTM), or a trichloropyrimidine dye such as those commercially available from Clariant under the tradename Drimarene X, with a suitable reactant containing an SRxe2x80x2 group and then reacting the intermediate dye obtained with a suitable reactant containing a Q group.
Due to the assymmetric nature of the pyrimidine heterocycle, dye compounds of the invention having a formula (I) wherein Z is a pyrimidine heterocycle can also be prepared by reacting a difluoromonochloropyrimidine dye such as those commercially available from Clariant under the tradenames Drimalan F (RTM) and Drimarene R or K (RTM), or a trichloropyrimidine dye such as those commercially available from Clariant under the tradename Drimarene X, with a suitable reactant containing a Q group and then reacting the intermediate dye obtained with a suitable reactant containing an SRxe2x80x2 group.
Dye compounds of the invention having a formula (I) wherein Z is a quinoxaline heterocycle can be prepared by reacting a dichloroquinoxaline dye such as those commercially available from Dystar under the tradename Levofix E (RTM), with a suitable reactant containing an SRxe2x80x2 group and then reacting the intermediate dye obtained with a suitable reactant containing a Q group.
The reactions of the starting dye compounds with the reactant containing an SRxe2x80x2 group are generally carried out at a pH of from about 7 to about 10, and at a temperature of about 0-5 C. The reactions of the intermediate dye compounds with the reactant containing a Q group are generally carried out at a pH of from about 5 to about 6 and at a temperature of from about 50-85C. In particular, the reactions of the intermediate dye compounds with the reactant containing a Q group are generally carried out at temperature of from about 50-55C when Z is triazine and 75-85 C when Z is pyrimidine.
When Z is pyrimidine, as detailed above, dye compounds of formula (I) can be prepared by reacting the starting dye compounds first with a suitable reactant containing a Q group and then reacting the intermediate dye obtained with a suitable reactant containing an SRxe2x80x2 group. In this case, the reactions of the starting dye compound with the reactant containing a Q group are generally carried out at a pH of from about 5 to about 6, and at a temperature of from about 40 to about 50C. The reactions of the intermediate dye compounds with the reactant containing the SRxe2x80x2 group are generally carried out at a pH of from about 5 to about 6, and a temperature of from about 50 to about 60C.
In general dyes having the formulae (II)-(V) can be prepared by using the same general chemistry as for dyes of formula (I) by reacting together suitable starting materials, and as exemplified below in Examples 10 to 14.
The dye compounds herein are suitable for dyeing and printing a wide variety of substrates, such as silk, leather, wool, polyamide, polyester fibers and polyurethanes, keratin fibres such as hair, and in particular cellulosic materials, such as the natural cellulose fibres, cotton, linen, hemp and the like, paper, and also cellulose itself and regenerated cellulose, and hydroxyl-containing fibres contained in blend fabrics, for example blends of cotton with polyester or polyamide fibres.
The dye compounds of the present invention can be applied and fixed to the substrate in various ways, in particular in the form of a solid mixture, aqueous dye solutions and printing pastes. Thus according to the present invention there is provided a dye composition comprising one or more of the dye compounds described herein together with any carrier material suitable for use in a dye composition.
Preferred dye compositions herein comprise an acidic buffer material. Any acidic buffer suitable for use in dye compositions can be used herein. An example of a suitable buffer is a mixed phosphate buffer.
When the dye composition herein is in the form of a paste a preferred ingredient is a thickening agent. Any suitable thickening agents suitable for use in dye compositions can be used herein.
When the dye composition is in the form of an aqueous solution or aqueous gel/paste, the dye composition preferably has a pH of about 5 or less, preferably from about 2 to about 3.
When the dye composition is being used for dyeing hair, the composition can comprise one or more of the compounds described herein either alone or in admixture with other well known hair dye compounds such as oxidative dyes, direct dyes, and the like.
The dyeing and printing processes which can be used with the dyes herein are conventional processes which are well known and which have been widely described in the technical and patent literature. The dye compounds herein are suitable for dyeing both by the exhaust method (long liquor) and also by the pad-dyeing method, whereby the goods are impregnated with aqueous, salt-containing or salt-free dye solutions and the dye is fixed after an alkali treatment or in the presence of alkali, if appropriate with the application of heat. The dye compounds herein are also suitable for the cold pad-batch method, after which the dye together with the alkali is applied to the pad-mangle and then fixed by several hours of storage at room temperature. After fixing, the dyeings or prints are thoroughly rinsed with cold and hot water, if appropriate with the addition of an agent acting as a dispersant and promoting the diffusion of the non-fixed portions.
Thus in accordance with another aspect of the present invention there is provided a use of the reactive dyes of the present invention for dyeing and printing substrates such as cotton, wool, nylon, silk, keratin, leather, paper and the like. The compounds herein can be used in methods of dyeing all of the substrates listed above by applying an aqueous solution of one or more of the reactive dyes of the present invention to the substrate to be dyed under suitable conditions of pH and temperature.
The following examples serve to illustrate the compounds and compositions of the present invention.